metal-organic compounds
Table 1
Hydrogen-bond geometry (A, ) for (I).
The water molecules are linked to the framework via O4—
1
ꢂ
˚
H4Cꢀ ꢀ ꢀO3 and O4—H4Dꢀ ꢀ ꢀO2(x, ꢁy + 2, z ꢁ ) hydrogen
2
bonds. Although the two-dimensional framework topologies
and the way they interpenetrate are similar to those in
complex (III) (Yang et al., 2009), there are some significant
differences in their structures. In (III), there are inter-
penetrating channels and the nodes of adjacent sheets are
parallel. For (I) and (II), however, there are square channels
which are not interpenetrated, and the nodes of the adjacent
sheets are in a line.
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
O4—H4Dꢀ ꢀ ꢀO2
0.87
0.84
2.18
2.14
3.044 (4)
2.973 (4)
172
168
O4—H4Cꢀ ꢀ ꢀO3v
1
2
Symmetry code: (v) x; ꢁy þ 2; z ꢁ .
Compound (I)
In summary, the most interesting feature in (I) and (II) is
the presence of a threefold interpenetrated framework with
square channels formed by L ligands and bdc2ꢁ dianions. This
behaviour may offer a route to new types of two-dimensional
framework structures.
Crystal data
3
˚
V = 2998 (3) A
Z = 4
[Cd(C8H4O4)(C22H22N4O2)]ꢀ2H2O
Mr = 686.98
Monoclinic, C2=c
Mo Kꢄ radiation
ꢀ = 0.79 mmꢁ1
T = 298 K
0.26 ꢄ 0.16 ꢄ 0.09 mm
˚
a = 17.450 (10) A
˚
˚
b = 15.480 (8) A
c = 12.636 (7) A
ꢃ = 118.545 (7)ꢂ
Experimental
Data collection
For the preparation of ligand L, KOH (1.40 g, 25 mmol) was added,
with stirring, to a solution of 1,2-bis(2-bromomethylphenoxy)ethane
(2.00 g, 5 mmol) and imidazole (0.69 g, 10 mmol) in anhydrous
tetrahydrofuran (50 ml) at ambient temperature. The mixture was
stirred for 12 h at ambient temperature. After removal of the solvent
under vacuum, the residue was purified on a silica-gel column using
DCM–MeOH (20:1 v/v) as the eluent to afford L as a white crys-
talline solid (yield 1.07 g, 2.86 mmol, 57.6%). IR (KBr pellet, ꢁ,
cmꢁ1): 3094 (m), 2948 (w), 2884 (w), 1601 (m), 1589 (m), 1502 (vs),
1473 (s), 1453 (s), 1430 (s), 1388 (w), 1355 (w), 1339 (w), 1286 (m),
1247 (vs), 1223 (s), 1190 (m), 1156 (w), 1112 (s), 1087 (s), 1055 (s),
1039 (m), 908 (w), 840 (w), 814 (s), 774 (s), 751 (vs), 686 (s), 661 (s),
631 (s), 575 (m), 453 (w); 1H NMR (300 MHz, CDCl3, TMS): ꢂ 7.50 (s,
2H, –C3H3N2), 7.33 (t, 2H, –C6H4–), 7.07 (d, 2H, –C6H4–), 6.98 (t, 2H,
–C3H3N2), 6.97 (t, 2H, –C6H4–), 6.96 (s, 2H, –C3H3N2), 6.90 (s, 2H, –
C6H4–), 5.08 (s, 4H, –CH2–), 4.30 (s, 4H, –CH2–). Elemental analysis
calculated for C22H22N4O2: C 70.59, H 5.88, N 14.97%; found: C 70.52,
H 5.78, N 15.09%.
Bruker SMART CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
Tmin = 0.822, Tmax = 0.933
8061 measured reflections
2944 independent reflections
2081 reflections with I > 2ꢅ(I)
Rint = 0.034
Refinement
R[F2 > 2ꢅ(F2)] = 0.040
wR(F2) = 0.097
S = 1.00
195 parameters
H-atom parameteꢁrs3 constrained
˚
Áꢆmax = 0.51 e A
Áꢆmin = ꢁ0.26 e A
ꢁ3
˚
2944 reflections
Compound (II)
Crystal data
3
˚
V = 2896.0 (10) A
Z = 4
[Co(C8H4O4)(C22H22N4O2)]ꢀ2H2O
Mr = 633.51
Monoclinic, C2=c
Mo Kꢄ radiation
ꢀ = 0.65 mmꢁ1
T = 298 K
0.26 ꢄ 0.16 ꢄ 0.09 mm
˚
˚
a = 17.612 (3) A
For the preparation of (I), L (3.74 mg, 0.01 mmol), Cd(NO3)2ꢀ4H2O
(3.08 mg, 0.01 mmol), H2bdc (1.66 mg, 0.01 mmol) and water (2 ml)
were sealed in a 5 ml glass tube. The mixture was heated at 453 K for
72 h under autogenous pressure. After the mixture had been allowed
to cool to room temperature (over a period of 50 h), yellow bar-
shaped crystals were isolated in 58.2% yield. IR (KBr pellet, ꢁ, cmꢁ1):
3135 (w), 3120 (w), 2950 (w), 2930 (w), 2875 (w), 1625 (m), 1602 (s),
1544 (vs), 1495 (s), 1451 (m), 1438 (m), 1387 (vs), 1293 (m), 1252 (s),
1232 (m), 1175 (w), 1111 (m), 1086 (s), 1067 (w), 1052 (w), 1035 (w),
1013 (w), 942 (m), 886 (w), 840 (s), 750 (vs), 711 (w), 657 (m), 643 (w),
531 (w), 435 (w). Elemental analysis calculated for C30H30CdN4O8: C
52.45, H 4.40, N 8.16%; found: C 52.32, H 4.49, N 8.25%.
b = 14.896 (3) A
˚
c = 12.711 (3) A
ꢃ = 119.724 (3)ꢂ
Data collection
Bruker SMART CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
Tmin = 0.849, Tmax = 0.944
7231 measured reflections
2547 independent reflections
1861 reflections with I > 2ꢅ(I)
Rint = 0.049
Refinement
R[F2 > 2ꢅ(F2)] = 0.052
wR(F2) = 0.127
S = 1.01
195 parameters
H-atom parameteꢁrs3 constrained
For the synthesis of (II), L (3.74 mg, 0.01 mmol), Co(NO3)2ꢀ6H2O
(3.37 mg, 0.01 mmol), H2bdc (1.66 mg, 0.01 mmol) and water (2 ml)
were sealed in a 5 ml glass tube. The mixture was heated at 423 K for
72 h under autogenous pressure. After the mixture had been allowed
to cool to room temperature (over a period of 36 h), red crystals were
isolated in 61.3% yield. IR (KBr pellet, ꢁ, cmꢁ1): 3139 (w), 3124 (w),
2953 (w), 2931 (w), 2878 (w), 1627 (m), 1603 (m), 1546 (vs), 1495 (s),
1451 (m), 1438 (m), 1401 (vs), 1293 (m), 1252 (s), 1235 (m), 1179 (w),
1108 (m), 1088 (m), 1069 (s), 1053 (w), 1034 (w), 1013 (w), 946 (m),
886 (w), 837 (m), 750 (vs), 711 (w), 659 (m), 647 (w), 532 (w), 435 (w).
Elemental analysis calculated for C30H30CoN4O8: C 56.88, H 4.77,
N 8.84%; found: C 56.79, H 4.85, N 8.91%.
˚
Áꢆmax = 0.36 e A
Áꢆmin = ꢁ0.29 e A
ꢁ3
˚
2547 reflections
Table 2
Hydrogen-bond geometry (A, ) for (II).
ꢂ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
O4—H4Dꢀ ꢀ ꢀO2
0.85
0.85
2.22
2.21
3.066 (4)
3.059 (4)
171
170
O4—H4Cꢀ ꢀ ꢀO3v
1
2
Symmetry code: (v) x; ꢁy þ 2; z ꢁ .
ꢃ
Acta Cryst. (2011). C67, m119–m122
Yuan et al.
[Cd(C8H4O4)(C22H22N4O2)]ꢀ2H2O and [Co(C8H4O4)(C22H22N4O2)]ꢀ2H2O m121